Polymeric color formers from hydroxyl polymers containing reactive ketaldone groups with reactive methylene and amino color formers



Patented July 26, 1949 POLYMERIC COLOR FORMERS FROM HY- DROXYL POLYMERSCONTAINING REAC- TIVE KETALDONE GROUPS WITH REAC- TIVE METHYLENE ANDAMINO COLOR FORMERS David Malcolm McQueen, Wilmington, Del., as-

signor to E. I. du Pont de Nemours & Company, Wilmington, Del., acorporation of Delaware No Drawing. Application March 26, 1946, SerialNo. 657,331

9 Claims. 1

This invention relates to polymeric color formers or dye intermediatesand, more particularly, to such intermediates which are capable ofcoupling with diazonium salts to give azo dyes or with oxidized primaryaromatic amine developing agents to given quinoneimine dyes or ammethinedyes.

An object of this invention is to provide new polymeric color formers ordye intermediates. A more specific object is to provide such dyeintermediates which can be used as coupling components in the arts offiber and film dyeing. A further object is to provide new hydrophilicpolymeric color formers which can be used as binding agents for silverhalides. Still other objects will be apparent from the followingdetailed description of the invention.

The above objects are attained by reacting a polymeric ketaldone with acolor former having a ketaldone-reactive group and recovering apolymeric color former. More specifically interpolymers of vinyl alcoholand polymerizable alpha, beta-ethylenically unsaturated ketaldones,which interpolymers contain recurring vinyl alcohol units and acyclicaldehyde or ketone groups, are reacted with a color former containingeither a reactive methylene group, a reactive primary or secondary aminoor amide group, or a thiol group whereby the carbon atom of the carbonylgroup of said aldehyde, or ketone becomes directly linked to the carbon,nitrogen, or sulfur atom of the said reactive groups. The polymerizableethylenically unsaturated ketaldones all have a vinyl or vinvlidenegroup attached to an oxocarbonylic group. Typical of these areketaldones of the structure where R and R are hydrogen or hydrocarbon.

The interpolymers of vinyl alcohol and the polymerizablealpha,beta-ethylenically unsaturated ketaldones useful in making thenovel polymeric color formers of this invention can be made by themethods described in assignees United States application Serial No.581,337 filed March 6, 1945 and now abandoned. The most practical ofsuch methods involves interpolymerizing a vinyl ester, e. g., vinylacetate, with allylidene diacetate in the presence of a catalyst whichcatalyzes the polymerization of vinyl compounds, e. g., organicperoxides including benzoyl peroxide, diethyl peroxide, and ammoniumpersulfate. In the allylidene diacetate, the aldehyde group potentiallypresent is inactive and may be referred to as a masked aldehyde" group.Because of the unreactivity of the aldehyde group in the polymer-formingreaction, the polymers are linear in character and may be of very highmolecular weight. The masking ester groups in the interpolymers can beeasily removed whereby recurring aldehyde groups are then formed. Thismay be accomplished by hydrolysis, saponification, or alcoholysisreactions as described in the aforesaid application.

The nature of the invention will be further illustrated with referenceto vinyl acetate/allylidene, diactetate copolymer containing the saidcomponents in an interpolymerization Weight ratio of 10 to 1 andprepared by the process described in Example 11 of aforesaid applicationSerial No. 581,337. This interpolymer is hydrolyzed to a vinylalcohol/acrolein interpolymer by dissolving it in an alcohol, e. g.,methanol or ethanol, or in a mixture of an alcohol and a hydrocarbon, e.g., toluene, and treatment with a suitable hydrolyzing agent orcatalyst, e. g., 10% NaOH or KOH solution. The interpolymers resultingfrom the hydrolysis reaction contain hydroxyl and aldehyde groups andare suitable for reaction with dye intermediates or color-formers ofvarious types which possess ketaldone-reactive groups. For example, theabove interpolymer is dissolved in aqueous alcohol solution and stirredat room temperature while adding an aqueous alkaline solution of a dyeintermediate, e. g., 1, -aminonaphthol. After stirring for three hoursat room temperature, the temperature is allowed to rise to 50 C. and ismaintained there for one hour. At the end of this time the solution iscooled and stirred while adding a nonsolvent for the interpolymer, suchas acetone. When the color-yielding polymer has been precipitated, it isfiltered and washed thoroughly with a solvent for the unreacted dyeintermediate. .With 1,5-aminonaphthol, such a solvent is a mixture ofalcohol and acetone in the ratio of '70 parts to 30 parts by Weight.'The resulting isolated interpolymer is a light-colored solid which maybe dissolved in water containing 10% ethanol by weight by heating andstirring at a temperature of to C. It contains a plurality ofaminonaphthol residues in each molecule of interpolymer. The aqueoussolution of the polymeric color former may thus be incorporated in anarticle in which color is desired, e. g., a photographic gelatin/silverhalide emulsion or a viscose fiber. Color is then produced, for example,by treatment with a diazonium salt or etc.

during color coupling development of latent silver esters andpolymerizable alphabeta-ethylenica'lly unsaturated ketaldones or theirprecursors in the form of the masked aldehydes, it is important that theinterpolymerizing components be present in ratios of approximately 1 molof the polymerizable ketaldone to -40 mols of the vinyl ester. As theketaldone component there may be used in certain cases monomeric vinylor vinylidene ketones, for example, methyl vinyl ketone or methylisopropenyl ketone. However, as pointed out previously, polymerizablealpha-betaethylenically unsaturated compounds containin masked aldehydegroups can also be interpolymerized with the vinyl ester with subsequenthydrolysis to free the hydroxyl and the aldehyde groups. The aldehydegroups may be masked prior to the interpolymerizing reaction byconverting them to diesters, acetals, ester-acetals, This is exemplifiedby the interpolymer of vinyl acetate and allylidene diacetate (acarboxylic acid diester of acrolein).

Prior to hydrolysis the vinyl ester/allylidene diacetate interpolymer isquite unsuitable for use in the present invention. However, afterhydrolysis both the hydroxyl groups, which impart a hydrophiliccharacter, and the aldehyde groups, which impart chemical reactivity,become available. It is important during the hydrolysis that alkalineconditions prevail, since under acid conditions the polymer reacts withitself to give an insoluble and infusible material.

Interpolymers suitable for reacting with the dye intermediates have therecurring units stru ture:

and after reaction with the color former the unit structure of thepolymeric molecule is:

where R and R are hydrogen or a hydrocarbon radical, m is a numberbetween and 50, and Q is 1 or 2 color-former nuclei.

Color formers suitable for reaction with the polymeric ketaldonescontain a group of the structure where n is 1 or 2, and may also containa primary amino group. Compounds containing such a structural groupinclude active methylene compounds, e. g., acylacetamides, acylaceticacid esters, cyanoacetic acid esters, cyanoacetic acid amides, andpyrazolones; aminophenols, aminopyrazolones, and aminoacylacetamides.

During the condensation, reaction water is eliminated by reaction of theketaldone group and the reactive methylene group (CH2--) or the primaryamino group. The exact structure of the polymeric color former compoundsformed is not known for certainty and is impossible to ascertain in apolymeric molecule of this type. By analogy with reactions involvingmonomeric compounds of these structures, the possible structuralformulae of the color-formin portion of the polymeric color formers ofthis invention may be shown as follows:

R (l) --CHs-l and Z 2) --0B can ii cna" for reactive methylene colorformers and R (8) CH:( J-

and Q L -cm-' Nnt' NH- for color formers having one ketaldone-reactiveamino group. When monomeric compounds containing both reactive methylene(CH2) groups and primary amino (--NH2) groups are condensed,combinations of the above linkages may occur. In formulae (1), (2), (3),and (4) R and R are hydrogen or a hydrocarbon radical; R"C correspondsto the same radical in a reactive methylene compound of the formulawhere R"C is the residue of the reactive methylene compound aftereliminating the two hydrogen atoms of the reactive methylene group InFormula (2) R" has the same significance as in Formula (1). In this casetwo molecules of a reactive methylene compound react with each carbonylgroup of the polymer.

In Formula (3), ==NQ corresponds to the same radical of a color formerof the formula of this invention contemplates the formation of polymericdye intermediates through reaction of thepolymeric ketaldone with amonomeric colorformer or dye intermediate through the coupling function.These polymeric color formers are used in silver halide emulsion layers.Upon exposure and color development, a water-insoluble monomeric dye isformed at the image areas. By treatment with a hydrolytic agent,splitting of the uncoupled polymeric dye intermediate occurs withconsequent removal of the water-soluble monomeric dye intermediate fromthe film. Thus the final film contains no uncoupled dye intermediateswhich may give rise to color instability. I

In the following examples all parts are given in terms of weight, alltemperatures are centigrade, and all operations involvinglight-sensitive materials are. carried out in the absence of actinicradiation. These examples are intended as illustrative only and shouldnot be conceived as limiting the invention in any way.

Example I A mixture of 25 parts of hydrolyzed vinyl acetate/allylidenediacetate interpolymer (mole ratio 10/1 described in Example 11 ofapplication Serial No. 581,337), 17 parts of 1-phenyl-3-methyl-fi-pyrazolone, 0.5 part of sodium methylate and 150 parts ofdioxane is heated and stirred at 70 for four hours. The solid iscollected on a filter and washed repeatedly with methanol to removeunreacted 1-phenyl-3-methyl-5-pyraz0- lone. The granular polymer is thendried. It has the following probable unit structure:

LL i3 When coupled with oxidized diethyl-p-phenylenediamine a brightmagenta dye is produced.

Example II A mixture of 62.5 parts of methanol-wet (40% solids)hydrolyzed vinyl acetate/allylidene diaoetate interpolymer (mole ratioabout 20/1 prepared by the method described in Example II of applicationSerial No. 581,337) 5 parts of 1- m-amino-phenyl-3-methyl-5-pyrazolone,44.5 parts of 5% sodium hydroxide, 45 parts of water, and 126 parts ofethanol is heated at 80 for four hours. Complete solution takes place inabout one hour. The reaction mixture is cooled and diluted with 2000parts of methanol. About ten parts of acetic acid is then added and thepolymer precipitates as small granules. It is collected on a filter andthen washed by decantation in four changes of ethanol. After drying, 25parts of light tan solid is obtained. This polymer has the followingprobable unit structure:

em-on A solution is prepared by stirring at 70 for one hour ten parts ofthis polymer, 47 parts of ethanol, and 142 parts of water. To one-halfof this solution is added 31 parts of 3N ammonium bromide and two partsof 0.5N potassium iodide. The mixture is stirred at 40 while adding asolution of 29 parts of 3N silver nitrate, 50 parts of water, and 17parts of 28% ammonium hydrox ide during one minute. After stirring for atotal of one-half hour, the emulsion is coagulated by the addition of 75parts of 10% sodium sulfate solution. The precipitate is washed inrunning water for one hour after which the excess water is drained off.The emulsion is redissolved by stirring at 65 with a mixture of 20 partsof ethanol and 60 parts of water for 30 minutes. The remainder of theoriginal polymer solution is then added and the solution stirred 15minutes longer. After cooling to 30, the emulsion is coated onbaryta-sized white paper and on cellulose acetate film base. Theresulting paper and film are exposed to light from an object to formlatent images, then developed in a solution made by admixing thefollowing components:

Parts p-Aminodiethylaniline hydrochloride 2 Sodium sulfite (anhydrous)10 Sodium carbonate (anhydrous) 20 Potassium bromide 2 Water to make1000 The paper and film are then washed, bleached in 4% potassiumferricyanide, fixed in 25% sodium thiosulfate and washed. The resultingpaper and film contain a bright, strong magenta negative dye image.

Example III A mixture of 19 parts of p-aminoacetoacetanilide, 500 partsof ethanol, parts of water,

and 60 parts of hydrolyzed vinyl acetate/ally]- CHrCH Torn-oni- L ii.

The material is incorporated into a photographic emulsion which issubsequently coated on a support, exposed, and developed as described inExample II to give a yellow dye image.

Example IV An interpolymer of vinyl acetate and methyl vinyl ketone oleratio /1) is made as follows: A mixture of 1 2 parts of vinyl acetate,14 parts of methyl vinyl 'ketene, 2 parts of ammonium persulfate, 0.2part of sodium blsulflte, 6 parts of sodium dodecyl' sulfate, and 600parts of water is shaken at 40 for 16 hours in a sealed reactor. Theemulsion is coagulated with sodium chloride solution, washed and driedto give 186 parts of polymer. This product is hydrolyzed by dissolvingit in 1000 parts of methanol containing 18 parts of potassium hydroxideand heating at the reflux temperature for twohours. The polymer whichprecipitates is collected on a filter, washed with methanol, and dried.

One hundred parts of the hydrolyzed vinyl acetate/methyl vinyl ketoneinterpolymer, 1000 parts of ethanol, 200 parts of water, 20 parts of1-m-aminophenyl-3-methyl 5 pyrazolone, and a 100 parts of 5% sodiumhydroxide is heated at 80 for five hours. The reaction mixture iscooled, neutralized with acetic acid and the resulting polymer isprecipitated by the addition of 1000 parts of methanol with stirring.The solid is collected on a filter and washed thoroughly with methanol.After drying, 110 parts of light tan powder are obtained. This materialgives a magenta color when coupled with oxidizeddiethylp-phenylenediamine. When coupled with diazotized sulfanilic acida bright yellow dye is produced.

In place of the polymeric ketaldones listed in the examples, there maybe used hydrolyzed interpolymers of vinyl esters with 2-methylallylidenediacetate, 2-phenyl allylidene diacetate, allylidene acetate-chloride,allylidene acetate-ethoxide, allylidene propionate-propoxide, 2-chloroallylidene diacetate, allylidene dipropionate, allylidene dibenzoate,allylidene benzoate-acetate, allylidene benzoate-ethoxide, ethyl'vinylketone, methyl isopropenyl ketone, phenyl vinyl ketone, and ethylisopropenyl ketone. Other hydrolyzable vinyl esters can be used as theester component but for reasons of convenience and economy vinyl acetateis preferred. Suitable additional vinyl esters include vinylchloroacetate. vinyl propionate, and vinyl isobutyrate.

Similarly, in place of the color formers of the examples one maysubstitute others including mamino-phenol, o-aminophenol,m-hydrc-xybenzamide, 1,5-amino-naphthol, J -acid, H-acid,2-hydroxy-4-methylthiophenol, 3 hydroxythionaphthene, andN-beta-naphthylhomophthalimide.

Similarly a novel class of polymeric acylacetamide color formers areprovided by substituting for the particular acetoacetanilide of ExampleI other such amides having a different acyl radical RCO- attached to theCHzCONH- radical. Such class may be typified by the general formulaRCO-CHzCO-NH-Rfi-X where RC0 is an acyl radical and R is an aryleneradical, e. g., phenylene, naphthylene, etc. and X is a ketaldonereactive group. Suitable acyl radicals include those of aliphatic,cycloalpihati-c, aromatic :and heterocyclic compounds. Among theacylacetanilides which can be reacted with the polymeric aldehydes asdisclosed in Example III areacetoacet-p-bromanilide,acetoacet-2-chlcranilide, acetoacet 2,4 dichloranilide,acetoacet-2,5-dichloranilide, acetoacetm-nitroanilide,o-methoxyacetoacetanilide, p-hydroxyacetoacetanilide, acetoacet panisidide, acetoacet-2-bromo p phenetidide, acetoacet-paminoanilide,acetoacet-m-dimethylaminoanilide, 2 acetoacetamino benzthiazole, 2acetoacetamino 4 methyl thiazole, furoylacetanilide, benzoylacetanilide,p-nitrobenzoylacetanilide, pamino-benzoylacetanilide.

The products have been found to be of a special value in photographicelements and processes of color photography utilizing color formingdevelopment. They may, for example, be added in aqueous solution to aphotographic polyvinyl alcohol/silver bromide emulsion and coated on asupport, such as paper or cellulose acetate film. After exposure to anobject scene, color is produced at the image areas by known means, suchas color development with N p-aminodiethylaniline, treatment with adiazoniiun salt followed by selective bleaching or the like. For colorphotography, as is well known, the materials must be selected to givethe subtractive colors of magenta, yellow and blue-green and it iscustomary to utilize three intermediates each of which produces one ofthe three necessary colors. For example, a film may be built up bycoating on a cellulose nitrate film base (1) a polyvinyl alcohol/silverhalide emulsion containing a reaction product of a vinylalcohol/acrolein interpolymer (mole ratio 20/1) with a1,5-aminonaphthol, (2) a clear polyvinyl alcohol separator, (3) apolyvinyl alcohol/silver halide emulsion containing the reaction productof a vinyl alcohol/acrolein interpolymer (mole ratio 20/1) with1-m-aminophenyl-3- methyl-5-pyrazolone, (4) a layer of a yellowcolloidal silver dispersed in polyvinyl alcohol, and (5) a polyvinylalcohol/silver halide emulsion containing the reaction product of avinyl alcohol/acrolein interpolymer (mole ratio 20/1) with(p-aminobenzoyl)acetanilide. The sensitivities of the emulsion layersare adjusted, as is known in the art, so that exposure to an objectscene gives color separation. Development first with ametol-hydroquinone developer, re-exposure and development withp-aminodiethylaniline, followed by treatment with potassium ferricyanidesolution and fixing ives a positive image in full color.

The new polymeric dye intermediates of the present invention are alsouseful in certain nonphotographic dyeing applications. Thus they areuseful in the process of United States patent ap-- plication of H.Woodward, Serial Number 411,262, filed September 17, 1941, now UnitedStates Patent No. 2,371,052, wherein polymeric dye intermediates arespun in viscose yarn or other fibers or filaments followed by generationof the dye by treatment with a diazotized aromatic amine. Dyes producedin this way possess outstanding washing and laundering fastness.

As many widely difierent embodiments of this invention can be madewithout departing from the spirit and scope thereof, it is to beunderstood that the invention is not to be limited except as defined bythe claims.

What is claimed is:

1. A polymeric color former obtained by the condensation of a polymericketaldone having recurring units of theformula:

where m is a number from 10 to 50, R and R are members of the groupconsisting of hydrogen and hydrocarbon radicals, with a pyrazolone colorformer, with the elimination of water.

3. A polymeric color former obtained by the condensation of a polymericketaldone having recurring units of the formula:

where m is a number from 10 to 50, R and R. are members of the groupconsisting of hydrogen and hydrocarbon radicals, with an acylacetamidecolor former, with the elimination of water.

4. A polymeric color former obtained by the condensation of a polymericketaldone having recurring units of the formula:

wheremisanumberirom10to50,RandR' are members of the group consisting ofhydrogen and hydrocarbon radicals, with an aminophenyl pyrazolone, withthe elimination of water.

5. A polymeric color former obtained by the condensation of a polymericketaldone having recurring units of the formula:

where m is a number from 10 to 50, R and R are members of the groupconsisting of hydrogen and hydrocarbon radicals, with an aminoacylacetaromatic amide, with the elimination of water.

8. A polymeric color former which has recurring units or the formula:

1. T E I I0 {Ont-EH1 C==0 OHIO/ where m is a number from 10 to 50.

7. A polymeric color former which has recurring units of the formula:

r 1 CHa-OH I Earl C-CHI 0:: O a where m is a number from 10 to 50.

8. A polymeric color former which has recurring units of the formula:

"I is I OHr-OH I #1 where m is a number from 10 to 50.

9. The process which comprises condensing a polymeric ketaldone havingrecurring units of the formula:

where m is a number from 10 to 50, R and R are members of the groupconsisting of hydrogen and hydrocarbon radicals, with a color formerselected from the group consisting of acylacetamides, acylacetic acidesters, cyanoacetic acid esters. cyanoacetic acid amides, pyrazolones,aminopyrazolones and aminoacylacetamides, in an aqueous alkaline medium.

DAVID MALCOLM MoQU'EEN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,332,897 DAlelio Oct. 26, 1943

